Hydrocracking catalyst comprising a layered clay-type crystalline aluminosilicate component, a group viii component and a thorium or uranium component, and process using said catalyst

ABSTRACT

A hydrocracking catalyst comprising a layered clay-type crystalline aluminosilicate cracking component, 0.01 to 2.0 weight percent, based on said cracking component and calculated as the metal, of a hydrogenating component selected from platinum and compounds thereof, palladium and compounds thereof, rhodium and compounds thereof, ruthenium and compounds thereof, and iridium and compounds thereof, and 0.01 to 5.0 weight percent, based on said cracking component and calculated as the metal, of a hydrogenating component selected from the group consisting of thorium and compounds thereof and uranium and compounds thereof, and processes using said catalyst.

United States Patent [72] Inventor Sigmund M. Csicsery Lafayette, Calif.

[21] Appl. No. 863,976

[22] Filed Oct. 6, 1969 [45] Patented Nov. 2, 1971 73] Assignee ChevronResearch Company San Francisco, Calif. The portion of the term of thepatent subsequent to Dec. 15, 1987, has been dlsclaimed.

[54] I-IYDROCRACKING CATALYST COMPRISING A LAYERED CLAY-TYPE CRYSTALLINEALUMINOSILICATE COMPONENT, A GROUP VIII COMPONENT AND A THORIUM ORURANIUM COMPONENT, AND PROCESS USING SAID Primary Examiner-Delbert E.Gantz Assistant Examiner-R. M. Bruskin Attorneys-A. L. Snow, F. E.Johnston, G. F. Magdegurger, C.

.l. Tonkin and Roy H. Davies ABSTRACT: A hydrocracking catalystcomprising a layered clay-type crystalline aluminosilicate crackingcomponent, 0.01 to 2.0 weight percent, based on said cracking componentand calculated as the metal, of a hydrogenating component selected fromplatinum and compounds thereof, palladium and compounds thereof, rhodiumand compounds thereof, ruthenium and compounds thereof, and iridium andcompounds thereof, and 0.01 to 5.0 weight percent, based on saidcracking component and calculated as the metal, of a hydrogenatingcomponent selected from the group consisting of thorium and compoundsthereof and uranium and compounds thereof, and processes using saidcatalyst.

HYDROCRACKING CATALYST COMPRISING A LAYERED CLAY-TYPE CRYSTALLINEALUMINOSILICATE COMPONENT, A GROUP VIII COMPONENT AND A THORIUM ORURANIUM COMPONENT, AND PROCESS USING SAID CATALYST INTRODUCTION Thisinvention relates to catalytic hydrocracking of hydrocarbons, includingpetroleum distillates and solventdeasphalted residua to producehigh-value fuel products, including gasoline.

PRIOR ART It is well known that a wide variety of crystalline zeoliticmolecular sieves may be used as the cracking component of hydrocrackingcatalysts. It is also well known that the preferred, and most commonlyused, hydrogenating components associated with these zeolitic crackingsupports are platinum and palladium. Rabo et al. U.S. Pat. No.3,236,76l, for example, provides a particular type of decationizedzeolitic molecular sieve catalyst, which may be used in some reactionswithout added metals, and in some reactions with added metals. Thevarious applicable reactions are isomerization, reforming, cracking,polymerization, alkylation, dealkylation, hydrogenation, dehydrogenationand hydrocracking.

It is also known that a crystalline zeolitic molecular sieve crackingcomponent, while relatively insensitive to organic nitrogen compoundsand ammonia, has a well-ordered and uniform pore structure as a resultof the crystal structure having bonds that are substantially equallystrong in three dimensions. This provides definite limitations on theaccess of reactant molecules to the interiors of the pores.

It is also known, particularly from Granquist U.S. Pat. No. 3,252,757,that a relatively new layered crystalline aluminosilicate mineral thathas been synthesized has the empirical formula xsio zAl o zmABzxl'l o,where the layer lattices comprise said silica, said alumina, and said B,and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F OH 5&0"and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50 percent relative humidity, silicaalumina saidmineral being characterized by a d spacing at said humidity within therange which extends from a lower limit of about 10.4 A. to an upperlimit of about 12.0 A. when A is monovalent, to about 14.7 A. when A isdivalent, and to a value intermediate between 12.0 A. and 14.7 A. when Aincludes both monovalent and divalent cations. Upon drying andcalcination whereby all or substantially all of the water is removed,said d spacing changes because of structural contraction of the mineral.The equivalent of an exchangeable cation, A, in said catalyst may bechosen from the group consisting of H", NHJ, Na Li K, ACa, %Mg liSr, andB and .m U!. li 9 9 Said synthetic aluminosilicatemineralisalayeredclay-type crystalline aluminosilicate, which term as used herein isintended to include dehydrated forms of said synthetic mineral, similarsynthetic minerals, and corresponding identical and similar naturalminerals.

Said aluminosilicate mineral, in the dehydrated (calcined) form, isknown from U.S. Pat. No. 3,252,889 to have application as a component ofa catalytic cracking catalyst; however, applications of said mineral asa component of a hydrocracking catalyst have not been disclosedheretofore, except in other patent applications of the assignee of thepresent application.

OBJECTS In view of the foregoing, objects of the present inventioninclude providing a novel catalyst useful for hydrocracking, and a novelhydrocracking process using said catalyst, said catalyst:

1. having a cracking component less sensitive to nitrogen poisoning thansilica-alumina gel;

2. Having a cracking component that is crystalline in structure, havingpores elongated in two directions, contrary to the pores of crystallinezeolitic molecular sieves, and therefore having less reactant accesslimitations than the pores of such molecular sieves;

3. Having a first hydrogenating component providing increased activityand stability to said catalyst, compared with a similar catalyst notcontaining said component;

4. Having a second hydrogenating component providing additionalstability to said catalyst, compared with the same catalyst whichcontains said first hydrogenating component but not said secondhydrogenating component.

It is a further object of the present invention to provide variousembodiments of a hydrocracking process using a catalyst having theaforesaid characteristics, including methods of further improvingcatalyst stability, and methods of operating the hydrocracking processin an integrated manner with other process units to achieve variousadvantageous results.

The present invention will best be understood, and further objects andadvantages thereof will be apparent, from the following description whenread in connection with the accompanying drawing.

DRAWING In the drawing, FIG. 1 is a diagrammatic illustration ofapparatus and flow paths suitable for carrying out the process ofseveral of the embodiments of the present invention, includingembodiments wherein a hydrofining zone precedes the hydrocracking zone,and embodiments wherein a selected fraction from the hydrocracking zoneis catalytically reformed;

FIG. 2 is a diagrammatic illustration of apparatus and flow pathssuitable for carrying out the process of additional embodiments of thepresent invention, including embodiments wherein a hydrofining zoneprecedes a hydrocracking zone in a single reactor shell, and embodimentswherein a selected fraction from the hydrocracking zone is catalyticallycracked.

STATEMENT OF INVENTION It has been found that a catalyst comprising alayered claytype crystalline aluminosilicate cracking component, forexample the layered synthetic clay-type crystalline aluminosilicatemineral of Granquist U.S. Pat. No. 3,252,757, in dehydrated form, ahydrogenating component selected from platinum and compounds thereof,palladium and compounds thereof, rhodium and compounds thereof,ruthenium and compounds thereof, and iridium and compounds thereof, inan amount of 0.0] to 2.0 weight percent, calculated as metal, and 0.0lto 5.0 weight percent, calculated as metal and based on said crackingcomponent, of a hydrogenating component selected from the groupconsisting of thorium and compounds thereof and uranium and compoundsthereof, has all of the desirable catalyst attributes listed underObjects above, and, therefore, in accordance with the present inventionthere is provided such a catalyst and a hydrocracking process using sucha catalyst. It has been found that the catalyst of the present inventionsurprisingly provides advantages over the Rabo et al. platinum orpalladium on molecular-sievehydrocracking catalyst, while unexpectedlybeing free from disadvantages that the art would lead one to expect. lnparticular, in the catalyst of the present invention: l) the presence ofthe thorium or uranium component results in a catalyst of higherstability than a catalyst that is identical, except that contains nosuch component; and (2) the presence of the component selected fromplatinum and compounds thereof, palladium and compounds thereof, iridiumand compounds thereof, rhodium and compounds thereof and ruthenium andcompounds thereof results in a catalyst of higher activity and stabilitythan a catalyst that is identical except that contains no such GroupVlll component.

In accordance with the present invention, therefore, there is provided ahydrocracking catalyst comprising a layered, claytype crystallinealuminosilicate cracking component, 0.01 to 2.0 weight percent, based onsaid cracking component and calculated as the metal, of a hydrogenatingcomponent selected from platinum and compounds thereof, palladium andcompounds thereof, iridium and compounds thereof, rhodium and compoundsthereof and ruthenium and compounds thereof, and 0.01 to 5.0 weightpercent, based on said cracking component and calculated as the metal,of a hydrogenating component selected from thorium and compounds thereofand uranium and compounds thereof, said cracking component having, priorto drying and calcining of said catalyst, the empirical formula nSiO,:AlO :mAB:xl-l O where the layer lattices comprise said silica, saidalumina, and said B, and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valencenotgreater than 2, and is external to the lattice,-

B is chosen from the group of negative ions which consists of F, OH,5&0" and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50 percent relative humidity, said mineral beingcharacterized by a d spacing at said humidity within the range whichextends from a lower limit of about 10.4 Angstroms to an upper limit ofabout 12.0 Angstroms when A is monovalent, to about 14.7 Angstroms whenA is divalent, and to a value intermediate between 12.0 Angstroms and14.7 Angstroms when A includes both monovalent and divalent cations.

Further in accordance with the present invention there is provided acatalyst effective for various hydrocarbon conversion reactions,including hydrocracking, hydrodesulfurization, hydrodenitrification,hydrogenation and hydroisomerization, comprising:

A. A dehydrated layer-type, crystalline, claylike mineral crackingcomponent which prior to dehydration has the empirical formula nSio zAlO zmABurH o, where the layer lattices comprise said silica, saidalumina, and said B, and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OH,V20" and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50 percent relative humidity, said mineral beingcharacterized by a d spacing at said humidity within the range whichextends from a lower limit of about 10.4 A. to an upper limit of about12.0 A. when A is monovalent, to about 14.7 A. when A is divalent, andto a value intermediate between 12.0 A. and 14.7 A. when A includes bothmonovalent and divalent cations, and

B. A hydrogenating component selected from platinum and compoundsthereof, palladium and compounds thereof, rhodium and compounds thereof,ruthenium and compounds thereof, and iridium and compounds thereof, inan amount of 0.01 to 2.0 weight percent, based on said crackingcomponent and calculated as metal, and a hydrogenating componentselected from thorium and compounds thereof and uranium and compoundsthereof, in an amount of 0.01 to 5.0 weight percent, based on saidcracking component and calculated as metal.

Said cracking component may be present in said catalyst in an amount of10 to 99.9 weight percent, based on the total catalyst. If desired, saidcatalyst may further comprise a crystalline zeolitic molecular sievecracking component in the amount of 1 to 50 weight percent,'based on thetotal catalyst. The equivalent of an exchangeable cation, A, in saidcatalyst may be chosen from the group consisting of H*, NHf, Na, Li",K", 'rCa, fiMg %Sr**, and 'rBa, and mixtures thereof.

Said catalyst additionally may comprise a component selected from thegroup consisting of alumina and silica-alumina. When the catalystcomprises alumina or silica-alumina, Titania advantageously may bepresent also. When said catalyst comprises said additional component,preferably the catalyst is prepared by coprecipitation of allnoncrystalline components to form a slurry, followed by addition of thelayered clay-type crystalline aluminosilicate component (andadditionally a crystalline zeolitic molecular sieve component, ifdesired) to the slurry in particulate form, followed by filtering,washing and drying to produce a hydrogel matrix having said crystallinecomponent (or components) dispersed therethrough. Preferably in thefinished catalyst said crystalline component (or components) will be inthe ammonia or hydrogen form, and will contain substantially all of therequired hydrogenating metals. This result will be obtained if saidcrystalline component (or components), loaded with the hydrogenatingmetals required in the catalyst of the present invention, is added tothe slurry of other catalyst components at a pH of 5 or above.Alternatively, said crystalline component substantially in the hydrogenor ammonia form and substantially free of all catalytic loading metals(containing less than 0.2 weight percent of catalytic metal or metals)may be contained in the finished catalyst. This result will be obtainedif the crystalline component, in the ammonia, hydrogen or sodium form,is added to the slurry of other catalytic components, including thehydrogenating metals required in the catalyst of the present invention,at a pH of 5 or above.

Further in accordance with the present invention, there is provided ahydrocracking process which comprises contacting a hydrocarbon feedstockcontaining substantial amounts of materials boiling above 200 F. andselected from the group consisting of petroleum distillates,solvent-deasphalted petroleum residua, shale oils and coal tardistillates, in a reaction zone with hydrogen and the aforesaid catalystcomprising a layered clay-type crystalline aluminosilicate athydrocracking conditions including a temperature in the range 400 to 950F., a pressure in the range 800 to 3,500 p.s.i.g., a liquid hourly spacevelocity in the range 0.1 to 5.0, and a total hydrogen supply rate of200 to 20,000 s.c.f. of hydrogen per barrel of said feedstock, andrecovering from said reaction zone valuable products, includinggasoline. The hydrogen feedstock preferably contains less than 1,000ppm. organic nitrogen. A prior hydrofining step may be used, if desired,to reduce the feed nitrogen content to the preferred level; however,because of the superior nitrogen tolerance of the layered clay-typecrystalline aluminosilicate component, compared with silica-alumina, thehydrofining step need not accomplish complete nitrogen contentreduction, as further discussed hereinafter.

Further in accordance with the present invention, advantageous resultsare obtained by providing in the reaction zone, in addition to saidcatalyst comprising a layered claytype crystalline aluminosilicate, aseparate second catalyst comprising a hydrogenating component selectedfrom Group Vl metals and compounds thereof, a hydrogenating componentselected from Group Vlll metals and compounds thereof, and a componentselected from the group consisting of alumina and silica-alumina.Further in accordance with the present invention, said separate secondcatalyst may be located in said reaction zone in a bed disposed abovesaid catalyst comprising a layered clay-type crystallinealuminosilicate-cracking component. ln the embodiments of the presentinvention discussed in this paragraph, no other prior hydrofining stepgenerally will be necessary, because hydrofining is accomplished in onereaction zone concurrently with hydrocracking, together with somehydrogenation of aromatics.

Still further in accordance with the present invention, there isprovided a hydrocracking process which comprises sequentially contactinga hydrocarbon feedstock and hydrogen with a first bed of catalyst andthen with a second bed of catalyst, said catalyst beds both beinglocated within a single elongated reactor pressure shell, said first bedof catalyst being located in an upper portion of said shell, thecatalyst of saidfirst bed comprising a hydrogenating component selectedfrom the group consisting of Group Vl metals and compounds thereof andGroup VIII metals and compounds thereof, and a component selected fromthe group consisting of alumina and silica-alumina, the catalyst of saidsecond bed being said catalyst comprising a layered clay-typecrystalline aluminosilicate, maintaining said first bed of catalyst andsaid second bed of catalyst at a temperature in the range 400 to 950 F.and a pressure in the range 800 to 3,500 p.s.i.g. during saidcontacting, maintaining the total supply rate of said hydrogen into saidreactor shell from 200 to 20,000 s.c.f. of hydrogen per barrel of saidfeedstock, and recovering a gasoline product from the effluent of saidsecond bed of catalyst.

The hydrocracking zone of the process of the present invention may beoperated once through, or advantageously may be operated by recyclingthereto materials from the effluent thereof that boil above 200 F.,preferably above 400 P. All or a portion of these heavier materialsadvantageously may be catalytically cracked. The heavy gasoline fractionfrom the hydrocracking zone advantageously may be catalyticallyreformed.

HYDROCARBON FEEDSTOCKS The feedstocks supplied to the hydrocracking zonecontaining the catalyst comprising a layered clay-type crystallinealuminosilicate in the process of the present invention are selectedfrom the group consisting of petroleum distillates, solvent-deasphaltedpetroleum residua, shale oils and coal tar distillates. The feedstockscontain substantial amounts of materials boiling above 200 F.,preferably substantial amounts of materials boiling in the range 350 to950 F., and more preferably in the range 400 to 900 F. Suitable feedstocks include those heavy distillates normally defined as heavystraight-run gas oils and heavy cracked cycle oils, as well asconventional FCC feed and portions thereof. Cracked stocks may beobtained from thermal or catalytic cracking of various stocks, includingthose obtained from petroleum, gilsonite, shale and coal tar. Asdiscussed hereinafter, the feedstocks may have been subjected to ahydrofining and/or hydrogenation treatment, which may have beenaccompanied by some hydrocracking, before being supplied to thehydrocracking zone containing said catalyst comprising a 'ayeredclay-type crystalline aluminosilicate.

NITROGEN CONTENT OF FEEDSTOCKS While the process of the presentinvention can be practiced with utility when supplying to thehydrocracking zone containing a catalyst comprising a layered clay-typecrystalline aluminosilicate, hydrocarbon feeds containing relativelylarge quantities of organic nitrogen, for example several thousand partsper million organic nitrogen, it is preferred that the organic nitrogencontent be less than 1,000 parts per million; more preferably, 0.5 to Iparts per million. As previously discussed, a prior hydrofining step maybe used, if desired, to reduce the feed nitrogen content to thepreferred level. The prior hydrofining step advantageously may alsoaccomplish hydrogenation and a reasonable amount of hydrocracking.Because of the superior tolerance of the layered clay-type crystallinealuminosilicate component for organic nitrogen compounds, compared withsilica-alumina, the hydrofining step need not accomplish completeorganic nitrogen content reduction. Further, because of the superiortolerance of said component for ammonia, compared with silica-alumina,and because said component is more tolerant of ammonia than of organicnitrogen compounds, ammonia produced in the hydrofining zone either maybe removed from the system between the hydrofining zone and thehydrocracking zone containing the hydrocracking catalyst comprising saidcomponent, or may be permitted to pass into the hydrocracking zone alongwith the feed thereto.

SULFUR CONTENT OF FEEDSTOCK While the process of the present inventioncan be practiced with utility when supplying to the hydrocracking zone,containing a catalyst comprising a layered clay-type crystallinealuminosilicate, hydrocarbon feeds containing relatively largequantities of organic sulfur, it is preferable to maintain the organicsulfur content of the feed to that zone in a range of 0 to 3 weightpercent, preferably 0 to 1 weight percent.

Catalyst Comprising a Layered Clay-Type Crystalline AluminosilicateComponent, a Hydrogenating Component Selected from Platinum andCompounds Thereof, Palladium and Compounds Thereof, lridium andCompounds Thereof, Rhodium and Compounds Thereof, and Ruthenium andCompounds Thereof, and a Component Selected From Thorium and CompoundsThereof and Uranium and Compounds Thereof A. General The layeredclay-type crystalline aluminosilicate used in preparing the catalyst maybe any catalytically active layered clay-type aluminosilicate, althoughthe synthetic mineral, in dehydrated form, described above and inGranquist U.S. Pat. No. 3,252,757 is preferred. The hydrated mineraldescribed in Granquist U.S. Pat. No. 3,252,757 may be used duringcombination of the various catalyst components; upon drying andcalcination of the catalyst the mineral is converted to the dehydratedform. This component will be present in the catalyst in an amount of IDto 99.9 weight percent, based on the total catalyst.

The thorium and/or uranium hydrogenating component of the catalyst maybe present in the final catalyst in the form of the metal, metal oxide,metal sulfide, or a combination thereof. This component may be combinedwith the layered clay-type crystalline aluminosilicate crackingcomponent, or may be combined with other catalyst components in whichsaid cracking component is dispersed, or both. in any case, the thoriumand/or uranium component will be present in an amount of 0.01 to 5.0weight percent, based on said cracking component and calculated as themetal,

When a conventional crystalline zeolitic molecular sievecrackingcomponent is included in the catalyst, said molecular sieve-crackingcomponent may be of any type that is known in the art as a usefulcomponent of a conventional hydrocracking catalyst comprising a GroupVIII noble metal or noble metalcompound-hydrogenating component, Adecationized molecular sieve-cracking component is preferred. Especiallysuitable are faujasite, particularly Y-type and X-type faujasite, andmordenite, in the ammonia form, hydrogen fonn, alkaline earth-exchangedform, or rare earth-exchanged form.

The hydrogenating component of the catalyst that is selected fromplatinum, palladium, iridium, rhodium, ruthenium, and compounds ofplatinum, palladium, iridium, rhodium and ruthenium may be present inthe final catalyst in the form of the metal, metal oxide, metal sulfide,or a combination thereof. This component may be combined with thelayered clay-type crystalline aluminosilicate-cracking component, or maybe combined with other catalyst components in which saidaluminosilicate-cracking component is dispersed, or both. In any case,the component will be present in an amount of 0.0l to 2.0 weightpercent, based on said aluminosilicatecracking component and calculatedas the metal.

A preferred catalyst comprises a layered clay-type crystallinealuminosilicate-cracking component intimately dispersed in a matrix ofother catalytic components comprising alumina, silica-alumina, orsilica-alumina-titania. The thorium or uranium, or compound thereof, andthe platinum, palladium, iridium, rhodium or ruthenium, or compound ofplatinum, palladium, iridium, rhodium or ruthenium, or compound ofplatinum, palladium, iridium, rhodium or ruthenium, may be combined withsaid aluminosilicate-cracking component before the latter is dispersedin the matrix, or the thorium or uraniurn or compound thereof and theplatinum, palladium. iridium, rhodium, ruthenium, or compound ofplatinum, palladium, iridium, rhodium or ruthenium may be a portion ofthe matrix. Examples of suitable matrices, in addition to matricesconsisting of alumina or silica-alumina, include matrices comprising:(a) palladium or a compound thereof and thorium or a compound thereofand silica-alumina; (b) palladium or a compound thereof and thorium or acompound thereof and alumina; (c) palladium or a compound thereof anduranium or a compound thereof and alumina; (d) palladium or a compoundthereof and uranium or a compound thereof and silica-alumina; (e)platinum or a compound thereof and thorium or a compound thereof andalumina; (f) platinum or a compound thereof and uranium or a compoundthereof and silica-alumina; (g) thorium or a compound thereof andiridium or a compound thereof and alumina or silica-alumina.

B. Method of Preparation The layered clay-type crystallinealuminosilicate mineralcracking component of the catalyst may beprepared, in hydrated form, in the manner set forth in Granquist U.S.Pat. No. 3,252,757. This form of the mineral may be used to combine withthe other catalyst components; during drying and calcining of theresulting composition to produce the final catalyst, said mineral isconverted to the dehydrated form. Alternatively, the mineral may bedehydrated and then impregnated with desired compounds.

In the case wherein thorium or uranium or a compound thereof andplatinum, palladium, iridium, ruthenium, rhodium, or compound ofplatinum, palladium, iridium, ruthenium or rhodium are added directly tothe layered clay-type crystalline aluminosilicate-cracking component,impregnation using aqueous solutions of suitable hydrogenating metalcompounds or adsorption of suitable hydrogenating metal compounds areoperable methods of incorporating the hydrogenating compound orcompounds thereof into said aluminosilicate component. ion exchangemethods whereby the hydrogenating components are incorporated into saidaluminosilicate component by exchanging those components with a metalcomponent already present in said aluminosilicate component may be used.However, such methods require use of compounds wherein the metals to beintroduced into said aluminosilicate component are present as cations.

In the case wherein said aluminosilicate-cracking component first isdispersed in a matrix of other catalytic components and thorium oruranium or a compound thereof and platinum, palladium, iridium, rhodium,ruthenium, or a compound of platinum, palladium, iridium, rhodium orruthenium are introduced into the resulting composition, impregnationusing an aqueous solution of suitable hydrogenating component compoundsor adsorption of suitable hydrogenating component compounds are thepreferred methods.

The platinum, palladium, iridium, ruthenium or rhodium compound used inpreparing the catalyst may be any convenient compound, for exampleplatinum, palladium or iridium chloride, tetra ammino palladium nitrate,etc.

Where the layered clay-type crystalline aluminosilicate component, withor without addedhydrogenating components, is dispersed in a matrix ofother catalyst components, the dispersion may be accomplished bycogelation of said other components around said aluminosilicatecomponent in a conventional manner.

Following combination of the catalyst components, the resultingcomposition may be washed free of impurities and dried at a temperaturein the range 500 to l,200 F.,

preferably 900 to l,l50 F., for a reasonable time, for example 0.5 to 48hours, preferably 0.5 to hours.

The finished catalyst may be sulfided in a conventional manner prior touse, if desired. If not presulfided, the catalyst will tend to becomesulfided during process operation from any sulfur compounds that may bepresent in the hydrocarbon feed. As discussed elsewhere herein, theequilibrium degree of sulfiding at a given operating temperature will bedifferent than in a corresponding catalytic system wherein a noble metalcomponent alone is present, with no thorium or uranium being present.

SEPARATE HYDROFlNlNG CATALYST A. General As previously indicated,advantageous results are obtained by providing in the reaction zonecontaining the hydrocracking catalyst of the present invention aseparate second catalyst comprising a hydrogenating component selectedfrom Group Vl metals and compounds thereof, a

, hydrogenating component selected from Group VIII metals and compoundsthereof, and a support selected from the group consisting of alumina andsilica-alumina. Pellets or other particles of this separate secondcatalyst may be physically mixed with said hydrocracking catalyst, butpreferably are disposed in a separate catalyst bed located ahead of saidhydrocracking catalyst in the same reactor shell, eliminating interstagecondensation, pressure letdown and ammonia and hydrogen sulfide removal.ln a preferred arrangement using downflow of hydrocarbon feed, the bedof separate second catalyst is located above said hydrocracking catalystin the same reactor shell.

Where said separate second catalyst is located in the same reactor shellas the hydrocracking catalyst of the present invention, it is preferablypresent in an amount in the range of 10 to 40 volume percent of thetotal amount of catalyst in the reactor.

In an arrangement less preferred than the ones discussed above in thissection, the separate second catalyst may be located in a separatehydrofining reactor, operated under conventional hydrofming conditions,from the effluent-of which ammonia or hydrogen sulfide, or both, andalso hydrocarbon products, if desired, may be removed prior tohydrocracking the remaining hydrofmed feedstock in a subsequenthydrocracking reactor in the presence of the catalyst of the presentinvention.

in any of the arrangements discussed in this section, the separatesecond catalyst preferably has hydrofining activity and hydrogenationactivity, and even more preferably also has enough hydrocrackingactivity to convert 0.2 to 50, preferably 5 to 20, weight percent of thehydrocarbon feedstock to products boiling below the initial boilingpoint of the feedstock in a single pass. The hydrogenation activitypreferably is sufficient to saturate or partially saturate a substantialportion of the organic oxygen, nitrogen and sulfur compounds in the feedto water, ammonia and hydrogen sulfide.

Preferably, said separate second catalyst contains nickel or cobalt orcompounds thereof in an amount of l to l5 weight percent, calculated asmetal, and molybdenum or tungsten or compounds thereof, in an amount of5 to 30 weight percent, calculated as metal, with the remainder of thecatalyst consisting of alumina, or silica-alumina containing up to 50weight percent silica.

Particularly preferred examples of said separate second catalyst,comprising silica-alumina, are:

It has been found that use of said separate second catalyst increasesthe gasoline yield from the hydrocracking stage containing the catalystof the present invention, compared with the gasoline yield from thehydrocracking stage when the identical feed thereto has not been firstor concurrently processed in the presence of said separate secondcatalyst. The increased gasoline yield probably is related to thehydrogenation, in that more saturated hydrocarbon structures tend tocrack more easily.

B. Method of Preparation Said separate second catalyst may be preparedby any conventional preparation method, including impregnation of analumina or silica-alumina support with salts of the desiredhydrogenating component, or cogelation of all components, with thelatter method being preferred.

As previously pointed out, the hydrocracking catalyst of the presentinvention has activity and stability advantages over certainconventional hydrocracking catalysts. It has been found that use of saidseparate second catalyst in the abovedescribed arrangements furtherincreases the stability of the hydrocracking catalyst of the presentinvention, compared with the stability of the latter catalyst when theidentical feed thereto has not been first or concurrently processed inthe presence of said separate second catalyst.

OPERATING CONDITIONS The hydrocracking zone containing the catalyst ofthe present invention is operated at hydrocracking conditions includinga temperature in the range of 400 to 950 F., preferably 500 to 850 F., apressure in the range 800 to 3500 p.s;i.g., preferably 1,000 to 3,000p.s.i.g. and a liquid hourly space velocity in the range 0.1 to 5.0,preferably 0.5 to 5.0, and more preferably 0.5 to 3.0. The totalhydrogen supply rate (makeup and recycle hydrogen) to said zone is 200to 20,000 s.c.f., preferably 2,000 to 20,000 s.c.f., of hydrogen perbarrel of said feedstock.

Where a separate hydrofining zone, which also may accomplishhydrogenation and some hydrocracking, is located ahead of thehydrocracking zone containing the catalyst of the present invention, theoperating conditions in the separate hydrofining zone including atemperature of 400 to 900 F., preferably 500 to 800 F., a pressure of800 to 3,500 p.s.i.g., preferably 1,000 to 2,500 p.s.i.g., and a liquidhourly space velocity of 0.1 to 5.0 preferably 0.5 to 3.0. The totalhydrogen supply rate (makeup and recycle hydrogen) is 200 to 20,000s.c.f. of hydrogen per barrel of feedstock, preferably 2,000 to 20,000hydrogen per barrel of feedstock.

Where a separate bed of hydrofining catalyst is located above a bed ofthe hydrocracking catalyst of the present invention in the same reactorshell, the space velocity through the bed of hydrofining catalyst willbe a function of the space velocity through the hydrocracking catalystbed and the amount of hydrofining catalyst expressed as a volume percentof the total catalyst in the reactor. For example, where the hydrofiningcatalyst is 25 volume percent of the total catalyst in the reactor, andthe space velocity through the bed of hydrocracking catalyst is 0.5 thespace velocity through the bed of hydrofining catalyst will be 2.7.Accordingly, the space velocity through the bed of hydrofining catalystin the process of the present invention may range from 0. l to 45.0.

The operating conditions in the reforming zone and catalytic crackingzone employed in various embodiments of the present invention areconventional conditions known in the art.

PROCESS OPERATION WITH REFERENCE TO DRAWING Referring now to FIG. I ofthe drawing, in accordance with a primary embodiment of the presentinvention, a hydrocarbon feedstock as previously described, which inthis case may boil above 400 F., is passed through line 1 intohydrocracking zone 2, which contains a hydrocracking catalyst comprisinga layered clay-type crystalline aluminosilicate-cracking component, 0.01to 2.0 weight percent, based on said cracking component and calculatedas the metal, of platinum, palladium, iridium, ruthenium or rhodium, and0.0l to 5.0 weight percent, based on said cracking component andcalculated as the metal, of thorium or uranium. As previously discussed,said layered aluminosilicate component may be dispersed in a matrix ofother catalyst components, which matrix may contain all or a portion ofthe hydrogenating components. Also as previously discussed, a separatesecond catalyst, previously described, may be located in hydrocrackingzone 2. The feedstock is hydrocracked in hydrocracking zone 2 atconditions previously discussed, in the presence of hydrogen suppliedthrough line 3. From hydrocracking zone 2 an effluent is withdrawnthrough line 4, hydrogen is separated therefrom in separator 5, andhydrogen is recycled to hydrocracking zone 2 through line 6. Fromseparator 5, hydrocracked materials are passed through lines 7 and 8 todistillation column 9, where they are separated into fractions,including a C fraction which is withdrawn through line 10, a C -l F.fraction which is withdrawn through line 11, and a l80-400 F. fractionwhich is withdrawn through line 12.

Still referring to FIG. 1, in accordance with another embodiment of thepresent invention, the l80-400 F. fraction in line 12 is reformed underconventional catalytic reforming conditions in reforming zone 13, fromwhich a catalytic reformate is withdrawn through line 14.

Still referring to FIG. 1, in accordance with another embodiment of thepresent invention, a hydrocarbon feedstock which is to be hydrofinedand/or hydrogenated, and partially hydrocracked, if desired, in aseparate hydrotreating zone prior to being hydrocracked in hydrocrackingzone 2, is passed through line 15 to hydrotreating zone 16 containing acatalyst, as previously described, having hydrofining and/orhydrogenation activity. The feedstock is hydrotreated in zone 16 atconditions previously described, in the presence of hydrogen suppliedthrough line 17. The efliuent from hydrotreating zone 16 is passedthrough line 18 to separation zone 19, from which hydrogen separatedfrom the treated feedstock is recycled through line 20 to hydrotreatingzone 16. In zone 19, water entering through line 21 is used to scrubammonia and other contaminants from the incoming hydrocarbon stream, andthe ammonia, water and other contaminants are withdrawn from zone 19through line 22. The scrubbed feedstock is passed through line 8 todistillation column 9 and thence to hydrocracking zone 2.

Referring now to FIG. 2, a hydrocarbon feedstock as previouslydescribed, which in this case may boil above 400 F., is passed throughline 29 to hydrotreating zone 30 containing a catalyst, as previouslydescribed, having hydrofining and/orhydrogenation activity. Thefeedstock is hydrofined and/or hydrogenated, and partially hydrocracked,if desired, in zone 30, at conditions previously described, in thepresence of hydrogen supplied through line 31. The effluent from zone 30is passed through line 32, without intervening impurity removal, intohydrocracking zone 33, where it is hydrocracked in the presence of ahydrocracking catalyst comprising a layered clay-type crystallinealuminosilicatecracking component and 0.0l to 2.0 weight percent, basedon said hydrocracking component and calculated as the metal, ofplatinum, palladium, iridium, ruthenium or rhodium, and 0.0l to 5.0weight percent, based on said cracking component and calculated as themetal, of thorium or uranium. Said catalyst may contain other catalyticcomponents, and a separate second catalyst may be present in zone 33, asdescribed in connection with zone 2 in FIG. 1. Hydrotreating zone 30 andhydrocracking zone 33 may be located in separate reactor shells, whichmay be operated at different pressures. Alternatively, and in apreferred manner of operation, hydrotreating zone 30 and hydrocrackingzone 33 may be separate catalyst beds located in a single pressure shell34, and the effluent from zone 30 may be passed to zone 33 withoutintervening pressure letdown, condensation or impurity removal. Theeffluent from zone 33 is passed through line 35 to separation zone 36,from which hydrogen is recycled through line 37 to hydrotreating zone30. All or a portion of the recycled hydrogen may be passed through line38 to hydrocracking zone 33, if desired. In separation zone 36, waterentering through line 40 is used to scrub ammonia and other contaminantsfrom the incoming hydrocarbon stream, and the ammonia, water and othercontaminants are withdrawn from zone 36 through line 41. The effluentfrom zone 36 is passed through line 42 to distillation column 43, whereit is separated into fractions, including a C, fraction which iswithdrawn through line 44,'a C 480" F. fraction which is withdrawnthrough line 45, a l80-400 F. fraction which is withdrawn through line46, and a fraction boiling above 400 F. which is withdrawn through line47. The fraction in line 47 may be recycled through lines 48 and 49 tohydrocracking zone 33. All or a portion of the fraction in line 48 maybe recycled to hydrotreating zone 30 through line 50, if desired.

Still referringto FIG. 2, in accordance with another embodiment of the,present invention, the l80-400 F. fraction in line 46 may be passed to acatalytic reforming zone 55, where it may be reformed in the presence ofa conventional catalytic reforming catalyst under conventional catalyticreforming conditions to produce a catalytic reforrnate, which iswithdrawn from zone 55 through line 56.

Still referring to FIG. 2, in another embodiment of the presentinvention, all or a portion of the fraction in line 47 may be passedthrough line 57 to catalytic cracking zone 58, which may contain aconventional catalytic cracking catalyst and which may be operated underconventional catalytic crackingconditions, and from which acatalytically cracked effluent may be withdrawn through line 59.

EXAMPLES The following examples are given for the purpose of furtherillustrating the practice of the process of the present invention.However, it is to be understood that these examples are not intended inany way to limit the scope of the present invention.

EXAMPLE I A layered aluminosilicate-palladium catalyst (Catalyst A, acatalyst in accordance with the present invention) is prepared in thefollowing manner.

These starting materials are used:

1. 450 grams of layered clay-type aluminosilicate in finely dividedform.

2. 6.5 grams of tetra ammino palladium nitrate APd(NH,), ](NO dissolvedin l,l00 ml. or H 0.

The layered aluminosilicate in powder form is mixed with the tetraammino palladium nitrate solution, to form a pasty mass. The pasty massis dried in a vacuum oven for 6 hours at room temperature, then at200250 F. for approximately 16 hours. The resulting dried material iscrushed and impregnated with a solution of 9.45 g. of uranyl nitrate{UO,( NO ),,-6H,O], having a concentration sufficient to provide l.0weight percent uranium, calculated as the metal, in the final catalyst.The so-impregnated material is dried in the same manner as in theprevious drying step.

The resulting material is tabletted, and then calcined in flowing dryair for 4 hours at 460 F., then for 4 hours at 900 F. The resultingcatalyst upon analysis found to contain 0.5 weight percent palladium,calculated as metal, and 1.0 weight percent uranium, calculated asmetal.

EXAMPLE 2 A catalyst (Catalyst B, a catalyst in accordance with thepresent invention) was prepared exactly as in example 1, except that l l.l grams of thorium nitrate [Th(NO ),-4H O] was used instead of uranylnitrate, and the catalyst was prepared by coimpregnation with thepalladium compound and the thorium compound, rather than by successiveimpregnation.

The final catalyst contains 0.5 weight percent palladium, calculated asmetal, and 1.0 weight percent thorium, calculated as metal.

EXAMPLE 3 A catalyst (Catalyst C, a comparison catalyst) is preparedexactly as in example 1, except that ammonium molybdate is used insteadof uranyl nitrate. The final catalyst contains 0.5 weight percentpalladium, calculated as metal, and 0.5 weight percent molybdenum,calculated as metal.

EXAMPLE 4 The catalysts of the above examples are used to hydrocrack aportion of a light catalytic cycle oil feedstock of the followingdescription:

Gravity, AP! 29.7 Aniline Point, F. 94.9 Sulfur Content, p.p.m. 0.3

Nitrogen content, p.p.m. 0.l

PNA Analysis P 9.9 vol. 7c

N 52.6 vol.

A 37.5 vol.

ASTM D-l I60 Distillation ST/S 333MB 10/30 428/459 Activity, API

Catalyst A (U) Catalyst B Th) Catalyst C (Mo) Of these catalysts,Catalysts A and B are the superior catalysts.

CONCLUSIONS Applicant does not intend to be bound by any theory for theunexpected superior activity and stability of the catalysts of thepresent invention. However, he assumes that the favorable results arelargely attributable to: (l) a different, and more favorable,equilibrium at a given operating temperature for the system consistingof thorium or uranium metal, the various thorium or uranium oxides, thevarious thorium or uranium sulfides, platinum, palladium, rhodium,ruthenium or iridium, the various oxides of platinum, palladium,ruthenium or iridium, the various sulfides of platinum, palladium,rhodium, ruthenium or iridium, and sulfur and hydrogen, than for thesystem consisting of platinum metal, platinum oxide, platinum sulfide,sulfur and hydrogen, which provides a hydrocracking catalyst superior tothe Rabo et al. nobel-metal-containing catalyst; and (2) an interactionbetween the effects of thorium or uranium or a thorium or uraniumcompound and a layered clay-type crystalline aluminosilicate-craekingcomponent that produces more favorable hydrocracking results than areproduced by an interaction between the effects of thorium or uranium ora thorium or uranium compound and a crystalline zeolitic molecular sieveor a gel-type silica-alumina-cracking component. lclaim:

1. A hydrocracking catalyst comprising a layered clay-typealuminosilicate cracking component, 0.01 to 2.0 weight percent, based onsaid cracking component and calculated as the metal, of a hydrogenatingcomponent selected from platinum and compounds thereof, palladium andcompounds thereof, iridium and compounds thereof, ruthenium andcompounds thereof and rhodium and compounds thereof, and 0.01 to 5.0weight percent, based on said cracking component and calculated as themetal, of a hydrogenating component selected from thorium and compoundsof thorium and uranium and compounds of uranium, said cracking componenthaving, prior to drying and calcining of said catalyst, the empiricalformula nSiO,:Al,0;,:mAB:xl-l,0 where the layer lattices comprise saidsilica, said alumina, and said B, and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OH, &"and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50 percent relative humidity, said mineral beingcharacterized by a d spacing at said humidity within the range whichextends from a lower limit of about 10.4 Angstroms to an upper limit ofabout 12.0 Angstroms when A is monovalent, to about 14.7 Angstroms whenA is divalent, and to a value intermediate between 12.0 Angstroms and14.7 Angstroms when A includes both monovalent and divalent cations.

2. A catalyst as in claim 1, which further comprises a matrix containinga component selected from alumina gel and silicaalumina gel.

3. A catalyst as in claim 2, wherein said layered clay-type crystallinealuminosilicate-cracking component is in particulate form, and isdispersed through said matrix.

4. A catalyst as in claim 2, which further comprises Titania.

5. A catalyst as in claim 3, wherein said layered clay-type crystallinealuminosilicate-cracking component is substantially in the ammonia orhydrogen form and is substantially free of any catalytic metal ormetals, and wherein said hydrogenating components are contained in saidmatrix.

6. A catalyst as in claim 5, which further comprises Titania.

7. A catalyst comprising:

A. A dehydrated layer-type, crystalline, claylike mineralcrackingcomponent which prior to dehydration has the empirical formulanSiO,:Al,0 :mAB:xl-l 0, where the layer lattices comprise said silica,said alumina, and said B, and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OH,9&0" and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50 percent relative humidity, said mineral beingcharacterized by a d spacing at said humidity within the range whichextends from a lower limit of about 10.4 A. to an upper limit of about12.0 A. when A is monovalent, to about 14.7 A. when A is divalent, andto a value intermediate between 12.0 A. and 14.7 A. when A includes bothmonovalent and divalent cations, and

B. A hydrogenatin component selected from platinum and compoundsthereof, palladium and compounds thereof, rhodium and compounds thereof,ruthenium and compounds thereof, and iridium and compounds thereof, inan amount of 0.01 to 2.0 weight percent, based on said crackingcomponent and comgounds thereof, in an amount of 0.01 to 5.0 wei htpercent, ased on said cracking component and calculate as metal.

8. A catalyst as in claim 7, wherein said mineral is present in anamount of 10 to 99.9 weight percent, based on the total catalyst.

9. A catalyst as in claim 7, which further comprises a crystallinezeolitic molecular sieve component, in the amount of l to 50 weightpercent, based on the total catalyst.

10. A catalyst as in claim 7, wherein A is chosen from the groupconsisting of H", NHf, Li K, 'ACa /zMg kSr and VzBa and mixturesthereof.

11. A hydrocracking process which comprises contacting a hydrocarbonfeedstock containing substantial amounts of materials boiling above 200F. and selected from the group consisting of petroleum distillates,solvent-deasphalted petroleum residua, shale oils and coal tardistillates, in a reaction zone with hydrogen and the catalyst of claim11, at hydrocracking conditions including a temperature in the range 400to 950 F., a pressure in the range 800 to 3,500 p.s.i.g., a liquidhourly space velocity in the range 0.1 to 5.0 and a total hydrogensupply rate of 200 to 20,000 s.c.f. of hydrogen per barrel of saidfeedstock, and recovering from said reaction zone valuable products,including gasoline.

12. A process as in claim 11, wherein said catalyst further comprises acomponent selected from the group consisting of alumina gel andsilica-alumina gel.

13. A process as in claim ll, wherein said hydrocarbon feedstockcontains 0.5 to 1,000 ppm. organic nitrogen.

14. A process as in claim 11, wherein said reaction zone contains, inaddition to said catalyst, a separate second catalyst comprising ahydrogenating component selected from Group Vl metals and compoundsthereof, a hydrogenating component selected from Group VIII metals andcompounds thereof, and a component selected from the group consisting ofalumina and silica-alumina. V

15. A process as in claim 14, wherein said separate second catalyst islocated in said reaction zone in a bed disposed above said catalystcomprising a layered clay-type crystalline aluminosilicate-crackingcomponent.

16. A hydrocracking process which comprises sequentially contacting ahydrocarbon feedstock and hydrogen with a first bed of catalyst and thenwith a second bed of catalyst, said catalyst beds both being locatedwithin a single elongated reactor pressure shell, said first bed ofcatalyst being located in an upper portion of said shell, the catalystof said first bed comprising a hydrogenating component selected from thegroup consisting of Group Vl metals and compounds thereof and Group VIIImetals and compounds thereof and a component selected from the groupconsisting of alumina and silica-alumina, the catalyst of said secondbed being the catalyst of claim 1, maintaining said first bed ofcatalyst and said second bed of catalyst at a temperature in the range400 to 950 F. and a pressure in the range 800 to 3,500 p.s.i.g. duringsaid contacting, maintaining the total supply rate of said hydrogen intosaid reactor shell from 200 to 20,000 s.c.f. of hydrogen per barrel ofsaid feedstock, and recovering a gasoline product from the effluent ofsaid second bed of catalyst.

17. A process as in claim 16, wherein the efiluent from said second bedof catalyst is separated into fractions, including a light gasolinefraction, a heavy gasoline fraction, and a fraction boiling generallyhigher than said heavy gasoline fraction.

18 A process as in claim 17, wherein said heavy gasoline fraction iscatalytically reformed.

19. A process as in claim 17, wherein said fraction boiling generallyhigher than said heavy gasoline fraction is cata|ytically cracked.

t t t i 0

2. A catalyst as in claim 1, which further comprises a matrix containinga component selected from alumina gel and silica-alumina gel.
 3. Acatalyst as in claim 2, wherein said layered clay-type crystallinealuminosilicate-cracking component is in particulate form, and isdispersed through said matrix.
 4. A catalyst as in claim 2, whichfurther comprises Titania.
 5. A catalyst as in claim 3, wherein saidlayered clay-type crystalline aluminosilicate-cracking component issubstantially in the ammonia or hydrogen form and is substantially freeof any catalytic metal or metals, and wherein said hydrogenatingcomponents are contained in said matrix.
 6. A catalyst as in claim 5,which furtHer comprises Titania.
 7. A catalyst comprising: A. Adehydrated layer-type, crystalline, claylike mineral-cracking componentwhich prior to dehydration has the empirical formulanSiO2:A1203:mAB:xH20, where the layer lattices comprise said silica,said alumina, and said B, and where n is from 2.4 to 3.0 m is from 0.2to 0.6 A is one equivalent of an exchangeable cation having a valencenot greater than 2, and is external to the lattice, B is chosen from thegroup of negative ions which consists of F , OH , 1/2 0 and mixturesthereof, and is internal in the lattice, and x is from 2.0 to 3.5 at 50percent relative humidity, said mineral being characterized by a d001spacing at said humidity within the range which extends from a lowerlimit of about 10.4 A. to an upper limit of about 12.0 A. when A ismonovalent, to about 14.7 A. when A is divalent, and to a valueintermediate between 12.0 A. and 14.7 A. when A includes both monovalentand divalent cations, and B. A hydrogenating component selected fromplatinum and compounds thereof, palladium and compounds thereof, rhodiumand compounds thereof, ruthenium and compounds thereof, and iridium andcompounds thereof, in an amount of 0.01 to 2.0 weight percent, based onsaid cracking component and calculated as metal, and a hydrogenatingcomponent selected from thorium and compounds thereof and uranium andcompounds thereof, in an amount of 0.01 to 5.0 weight percent, based onsaid cracking component and calculated as metal.
 8. A catalyst as inclaim 7, wherein said mineral is present in an amount of 10 to 99.9weight percent, based on the total catalyst.
 9. A catalyst as in claim7, which further comprises a crystalline zeolitic molecular sievecomponent, in the amount of 1 to 50 weight percent, based on the totalcatalyst.
 10. A catalyst as in claim 7, wherein A is chosen from thegroup consisting of H , NH4 , Li , K , 1/2 Ca , 1/2 Mg , 1/2 Sr , and1/2 Ba and mixtures thereof.
 11. A hydrocracking process which comprisescontacting a hydrocarbon feedstock containing substantial amounts ofmaterials boiling above 200* F. and selected from the group consistingof petroleum distillates, solvent-deasphalted petroleum residua, shaleoils and coal tar distillates, in a reaction zone with hydrogen and thecatalyst of claim 1, at hydrocracking conditions including a temperaturein the range 400* to 950* F., a pressure in the range 800 to 3,500p.s.i.g., a liquid hourly space velocity in the range 0.1 to 5.0 and atotal hydrogen supply rate of 200 to 20,000 s.c.f. of hydrogen perbarrel of said feedstock, and recovering from said reaction zonevaluable products, including gasoline.
 12. A process as in claim 11,wherein said catalyst further comprises a component selected from thegroup consisting of alumina gel and silica-alumina gel.
 13. A process asin claim 11, wherein said hydrocarbon feedstock contains 0.5 to 1,000p.p.m. organic nitrogen.
 14. A process as in claim 11, wherein saidreaction zone contains, in addition to said catalyst, a separate secondcatalyst comprising a hydrogenating component selected from Group VImetals and compounds thereof, a hydrogenating component selected fromGroup VIII metals and compounds thereof, and a component selected fromthe group consisting of alumina and silica-alumina.
 15. A process as inclaim 14, wherein said separate second catalyst is located in saidreaction zone in a bed disposed above said catalyst comprising a layeredclay-type crystalline aluminosilicate-cracking component.
 16. AhydrOcracking process which comprises sequentially contacting ahydrocarbon feedstock and hydrogen with a first bed of catalyst and thenwith a second bed of catalyst, said catalyst beds both being locatedwithin a single elongated reactor pressure shell, said first bed ofcatalyst being located in an upper portion of said shell, the catalystof said first bed comprising a hydrogenating component selected from thegroup consisting of Group VI metals and compounds thereof and Group VIIImetals and compounds thereof and a component selected from the groupconsisting of alumina and silica-alumina, the catalyst of said secondbed being the catalyst of claim 1, maintaining said first bed ofcatalyst and said second bed of catalyst at a temperature in the range400* to 950* F. and a pressure in the range 800 to 3,500 p.s.i.g. duringsaid contacting, maintaining the total supply rate of said hydrogen intosaid reactor shell from 200 to 20,000 s.c.f. of hydrogen per barrel ofsaid feedstock, and recovering a gasoline product from the effluent ofsaid second bed of catalyst.
 17. A process as in claim 16, wherein theeffluent from said second bed of catalyst is separated into fractions,including a light gasoline fraction, a heavy gasoline fraction, and afraction boiling generally higher than said heavy gasoline fraction. 18A process as in claim 17, wherein said heavy gasoline fraction iscatalytically reformed.
 19. A process as in claim 17, wherein saidfraction boiling generally higher than said heavy gasoline fraction iscatalytically cracked.